CA2009471A1 - Hybrid plastic filling material - Google Patents
Hybrid plastic filling materialInfo
- Publication number
- CA2009471A1 CA2009471A1 CA002009471A CA2009471A CA2009471A1 CA 2009471 A1 CA2009471 A1 CA 2009471A1 CA 002009471 A CA002009471 A CA 002009471A CA 2009471 A CA2009471 A CA 2009471A CA 2009471 A1 CA2009471 A1 CA 2009471A1
- Authority
- CA
- Canada
- Prior art keywords
- meth
- treated
- weight
- light
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000463 material Substances 0.000 title description 27
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229930006711 bornane-2,3-dione Natural products 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011350 dental composite resin Substances 0.000 claims abstract description 4
- 239000011256 inorganic filler Substances 0.000 claims abstract description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 4
- -1 acrylic compound Chemical class 0.000 claims abstract description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims 2
- 239000000945 filler Substances 0.000 description 9
- 230000005764 inhibitory process Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 5
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229940094070 ambien Drugs 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZAFYATHCZYHLPB-UHFFFAOYSA-N zolpidem Chemical compound N1=C2C=CC(C)=CN2C(CC(=O)N(C)C)=C1C1=CC=C(C)C=C1 ZAFYATHCZYHLPB-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S522/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S522/908—Dental utility
Abstract
ABSTRACT OF THE DISCLOSURE
In a dental composite containing a polymer-izable (meth)acrylic compound, photoinitiator, acceler-ator, inorganic filler and conventional auxiliaries, the improvement wherein the composite by weight comprises about a) 10-50% of at least one monomer which contains at least 2 polymerizable (meth)acrylic acid groups, b) 5-80% of a glass or a glass ceramic which has an average particle size of between about 0.1 and 10 µm and has been post-treated with .gamma.-methacryloxy-propyltrLmethoxysilane up to a carbon content of between about 0.5 and 2.5% by weight, c) 2-10% of a surface-treated microfiller and d) 0.1-5% of a photoactivator consisting of a mixture of camphorquinone and p-dialkylamino-benzenesulphonamide. The composition has a long pot life and good surface color when cured.
* * *
In a dental composite containing a polymer-izable (meth)acrylic compound, photoinitiator, acceler-ator, inorganic filler and conventional auxiliaries, the improvement wherein the composite by weight comprises about a) 10-50% of at least one monomer which contains at least 2 polymerizable (meth)acrylic acid groups, b) 5-80% of a glass or a glass ceramic which has an average particle size of between about 0.1 and 10 µm and has been post-treated with .gamma.-methacryloxy-propyltrLmethoxysilane up to a carbon content of between about 0.5 and 2.5% by weight, c) 2-10% of a surface-treated microfiller and d) 0.1-5% of a photoactivator consisting of a mixture of camphorquinone and p-dialkylamino-benzenesulphonamide. The composition has a long pot life and good surface color when cured.
* * *
Description
2~
The invention relate~ to new light~curing dental compo~ite~, in particular tooth illing composites.
Light~curing tooth filling materials are known.
~hey con ist in general of one ox more (meth)acrylic resins, suxface-txeated fillers t photoactiv~tor~, accel-era~ors and au~iliaries (e.g. colorants, light ~tabil-izers) ~abilizers and the like). Filling materials are divided into tho~e which axe u~ed in the anterior teeth and tho~e which are used in the po~terior teeth. The latter frequently contain large amounts of inorganic fillsr to achieve suffi~ient wear resistance and good mschanical propertie~.
An essential requirement for a s~itable material is a sufficiently long pot life under ambient light (d~ylight).
The dentiYt must have enough time available to insert the material in the cavity and sh~pe it there a~
he sees fit. E~en during an extended duration of treat-ment by the dentist, for ex2mple in edge construction, the plastic filling material ~u~t not become ~olid under ambien~ light.
On the other hand, rapid and complete curing of the filling is expected to take place on expo~ure to the light of a dental lamp. ~he polymerization depths mu~t thu~ be as large as pos~ible and, at the ~ame tîme, no inhib~ion layer must fonm on the ~urface of the La A 26 557 - 1 ~
X~ 71 material.
A~ present, no composites are known which meet both requirements.
Many of the known filling materials have a pot lie which is much too short. If these materials are subjected to a test, ~uch a , for example, provided by D~ propo~al 0013922, they are often only processable up to 10 seconds. This is much too short, e~pecially for filling~ in the mola1 area, since thQre is a risk that the material is cured or partially polymerized during the processing and thus is damaged in a way not always discsrnible to the dentist. Other materials ha~e an adequate pot life, but the~e form a deep inhibition layer at the surfaceO When the materials are subjected to a test such as provided by the ~'Revision of ISO 4049, 1978", ~hese material~ ~how ~u~stantial discolorations on the surface. Moreover, the curing behavior of the filling materials often deteriorates even after a very short shelf-life, and the denti~t has no guarantee that th2y will cure completely.
The ob~ect of the present invention is to provide a ~torable light-curable plastic filling material, in the use of which, on the one hand, there i8 suf~icient time to allow the material to be carefully placed, but which, on the other hand, is also cured rapidly and completely upon exposure to the light of a commercial dental lamp.
It ha~ been found that the use of p-dialkylamino-benzene~ulphonamides as accelerators, together with camphorquinone in combination with surface-coated glass Le A 26 5~7 - 2 -fillers of a certain degree of silanization, and micro-filler~ and-commercial monomer and auxiliaries leads to filling ma~erials which have a long pot life but, on the other hand, cure rapidly and completely after expo~ure to the light of a dental lamp. Compared with known products, the~e materials do not ~how any deterioration in mechanical properties after ~torage for 2 years.
The light-curing dental compo~ites according to the inventionl in particular tooth filling composites, which contain one or more polymerizable (meth~acrylic compounds, photoinitiators, accelerators, inorganic filler~ and, if desired, conventional auxiliaries are characterized in that they contain:
a) 10-50~ by weight of one or more monomers which contain at least 2 polymerizable ~meth)acrylic acid groups, b) 5-80% by weight of a glass or a glass ceramic which has an average particle diameter of between 0.1 and lO ~m and ha~ been surface-treated with ~-meth-acryloxypropyltrimethoxysilane up to a carbon content of between 0.2 and :2.5% by weight, c) 2-10% by weight of a ~urface--treated microfiller and d) 0.1-5% by weight of a photoactivator consi~ting of a mixture of camphorquinone and p-dialkylamino-benzene~ulphonamide.
Ex~mpla3 of &uitable monomers are as ~ollows:
Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, l,12-dodecanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dime~h-acrylate, 2,2-bi~(p-(2'-hydroxy-3'-methacryloyloxy-Le A 26 557 - 3 -propoxy)phenyl)propane, 2,2-bis(p-(2'-methac~yloyloxy-ethoxy)phenyl)propane, trLmethylolpropane tri(meth)-acrylate, bis-(meth)acryloyloxyme~hyl)-tricyclo-[5.2.1.0Z6]decane according to Genman Offenlegungsschrift 2,931,925 and German Offenlegungsschrift 2,931,926, 1,3-di((meth)acryloyloxypropyl)-1,1,3,3-tretramethyl-disiloxane ana 1,3-bis(3-(me~h)acryloyloxyethylcarbamoyloxy-propyl)-1,1,3,3-te~r~nethyldisiloxane. MonomexR which at 13 mbar have a boilin~ point of mere than 100C are particularly preferred.
In the context of the pre~ent inYention, it i9 preferred to use mixtures of different (meth)acrylates according to the in~ention.
It is also possible to use mixtures of monomers which contain several comonomers.
Preferred light-curing dental composites accord-ing to the invention, in particular tooth filling com-posites t which contain one or more polymerizable (meth)-acrylic compound~, photoinitiators, accelerators, inorganic fillers and, if desired, conventional au~iliar-ies are characterized in that they contain a) 10-30~ by weight of one or more monomers which contain at least 2 polymerizable (meth)acrylic acid groups, b) 40-75~ by weight of a glas or a glass ceramic which ha~ a partlcle size of between 0.1 and 10 ~m and has been post-treated with ~-methacryloxypropyl~ri-methoxysilane up to a carbon cont~nt of between 0.5 and 2.5~ by weight, Le A 26 557 ~ 4 ~
c) 2-10% by weigh~ of a surface trea~ed microfiller and d) 0.1-5% by weight of a photoactivator consi~ting o a mix~ure of camphorquinone and p-dialkylamino-~enzenesulphonamide.
The examples which follow demonstrate the ad-vantages of the compo3ites according to the invention.
As already mentioned, the essential fQature ~f a plastic filling material is a sufficiently long pot life in combination with rapid and complete curing on exposure to the light of a dental lamp. This means that the polymerization depths should be as large as po sible. An inhibition layer on the ~urface of the cured pla~tic, which becomes visible as a ~trong surface discoloration in a test according to "Revi~ion of ISO 4049/1978"/ is a disadvantage; it must be avoided. Thu~, the optLmum composite sh~uld have long pot lives in ambient light, rapid and complete curing on exposure to the light of a dental lamp and no surface discoloration. This require-ment is met by the plastic ~illing materials according to the invention.
Example 1 (comparative e~ample3 1000 ~ of pa~te contain:
Bisphenol A diglycidyl dimethacrylate (BIS GMA): 128.725 g Triethylene glycol dimetha~rylate (TEGDMA) 105.330 g Surface-treated Ba glass filler, a~erage particle diameter 1.3 ~m 762.225 g Camphorquino~e/diethylaminoethyl acrylate a~ ~tar~er sy~tem: 1.010 g Auxil~rie~ and additives: 2.710 g Le A 26 55? 5 (2.38 g of ~TINUVIN P, 0.33 g of ~IONOL) Pot life of the paste in ambient light measured in accordance with DIN propoæal 0013922: 150 s Polymerization depth after an exposure of 60 s to the light of a dental lamp:6.5 mm Inhibition layer on the surf ace of the cured plastic filling material determined by a te~t as provided in "Revi~ion of ISO 40 49/1978 " I yes xample 2 (comparative ex~mple) 1000 g of paste containo BIS GMA; 62.00 g TEGDMA; 62.00 g Surface-treated Zn glass filler, average particle diameter 2.3 ~m 875.00 g ~uxiliari 5 and additives: 1.44 g (1.26 g of ~TINWIN P, 0.18 g of ~IONOL) Camphorquinone N,N-dLmethylamino-p-hydroxy-ethylbenzene as staxter system: 1.30 g Pot life of the paste in ambient light measuxed in accordance with DIN proposal 0013g~2: 50 s Polymerization depth after an exposure of 60 s to the light of a dental l~mp:5.9 mm Inhibition layer on the surface of the cured pla~tic filling mat~rial determined by ~ test a~ provided in "Revi~ion of ISO 4049/lg78"; yes Ex~mple 3 (compara~ive example) 1000 g ef paste contain~
BIS phenol~A PO/hex~methylene diisocyanate- 74.25 g ~EGDMA: 60.75 ~
.
Le_A 26 557 - 6 -2C3~ 7 Surface-treated Ba glass filler, average particle diameter 3 ~m 862.03 g ~uxiliarie~ and additi~es: 1.56 g (1.37 g of ~TINUVIN P, 0.19 g of ~IONOL) Camphorquinone/diethylaminoethyl methacrylate a~ starter sy~tem: 1.41 g Pot life of the ~aste in ambient light measured in accordance with DIN proposal 0013922: 30 5 Polymerization depth after an expo~ure of 60 ~ to the light of a dental l~mp: 6.5 mm Inhibition layer on the surface of ~he cured plastic filling material determined by a test a~ provided in "Revision of ISO 4049/1978": no Example 4 (comparative example) 1000 ~ of pa~te contain.
BIS GMA; 71.00 g TEGDM~; 71.00 g Surface-treated Zr ceramic filler, average par~icle diameter 2 ~m 854.83 g Auxiliaries and additi~e~: 1.65 g (1.45 g of ~TINUVIN P, 0.~0 g of ~IONOL) Camphorquinone N,N-dimethylamino-p-hydroxy-ethylbenzene (pre~ent in the monomer) 1.52 g Pot life of the paste in ambient light mea~ured in accordance with DIN propo~al 001392~: 15 s Pol~erization depth after an exposure of 60 5 to ~he light of a dental lamp: 4.7 mm Le A 26 S57 - 7 -z~
Inhibition layer on the surface of the cured plastic filling material determined by a test as provided in "Revision of ISO 404~/1978": no Example 5 (according to the invention) 1000 g of paste contain:
BIS GMA; 172.015 g TEGDMA; 74.008 g Surface-treated Ba glas~ filler, average particle diameter 1.2 ~m 749.486 g Camphorquinone/diallylsulphonamide as ~tarter sy~tem: 1.641 g ~uxiliaries and additives: 2.850 g (2.50 g of ~TINWIN P, 0.35 g of ~IONOL) Pot life of th~ pa~te in ambient light mea~ured in accord~nce with DIN proposal 0013922: 100 Polymerization depth after an exposure of 60 ~ to the light of a dental lamp: 7.7 mm Inhibition layer on the ~urfac~ of the cured plastic fillin~ material determined by a test a~ provided in "Revision of ISO 4049/1978": no The example~ listed clearly show that the com-posite according to the invention tExample 5) which contain3 ~he new starter system camphorquinone/diallyl 2~ suphonamide in combination with the surfacs-coated glass filler~ of a cer~ain degree of s.ilanization mee~s the required conditions. In addition to a long pot life in ambien~ light, rapid and complete curing ic achieved on exposure to the light of a dental lamp, while the cured plasti~ filling material does not ~how a ~urface di~-Le A 26 557 - 8 -2~ r~
coloration.
The material accordin~ to com-parative Example 1 ha a very long pot life in ambienk light, but the curing depths on exposure to the light of a dental lamp are small and at the same tlme a thick inhibition layer is iormed on the surface of the cured material.
The material~ according to ~xample~ 2, 3 and 4 have very short pot lives under ambient light.
The weight ratio of camphorquinone to diallyl-sulphonamide advantageously is from 4:1 to 1:4 and prefer-ably from 2:1 to 1:2.
It will be appreciated that the instant specification and claims are set forth by way of illustration and not limitation and that various modifications and changes may be made without departing from the spirit and scope of the present invention.
g _
The invention relate~ to new light~curing dental compo~ite~, in particular tooth illing composites.
Light~curing tooth filling materials are known.
~hey con ist in general of one ox more (meth)acrylic resins, suxface-txeated fillers t photoactiv~tor~, accel-era~ors and au~iliaries (e.g. colorants, light ~tabil-izers) ~abilizers and the like). Filling materials are divided into tho~e which axe u~ed in the anterior teeth and tho~e which are used in the po~terior teeth. The latter frequently contain large amounts of inorganic fillsr to achieve suffi~ient wear resistance and good mschanical propertie~.
An essential requirement for a s~itable material is a sufficiently long pot life under ambient light (d~ylight).
The dentiYt must have enough time available to insert the material in the cavity and sh~pe it there a~
he sees fit. E~en during an extended duration of treat-ment by the dentist, for ex2mple in edge construction, the plastic filling material ~u~t not become ~olid under ambien~ light.
On the other hand, rapid and complete curing of the filling is expected to take place on expo~ure to the light of a dental lamp. ~he polymerization depths mu~t thu~ be as large as pos~ible and, at the ~ame tîme, no inhib~ion layer must fonm on the ~urface of the La A 26 557 - 1 ~
X~ 71 material.
A~ present, no composites are known which meet both requirements.
Many of the known filling materials have a pot lie which is much too short. If these materials are subjected to a test, ~uch a , for example, provided by D~ propo~al 0013922, they are often only processable up to 10 seconds. This is much too short, e~pecially for filling~ in the mola1 area, since thQre is a risk that the material is cured or partially polymerized during the processing and thus is damaged in a way not always discsrnible to the dentist. Other materials ha~e an adequate pot life, but the~e form a deep inhibition layer at the surfaceO When the materials are subjected to a test such as provided by the ~'Revision of ISO 4049, 1978", ~hese material~ ~how ~u~stantial discolorations on the surface. Moreover, the curing behavior of the filling materials often deteriorates even after a very short shelf-life, and the denti~t has no guarantee that th2y will cure completely.
The ob~ect of the present invention is to provide a ~torable light-curable plastic filling material, in the use of which, on the one hand, there i8 suf~icient time to allow the material to be carefully placed, but which, on the other hand, is also cured rapidly and completely upon exposure to the light of a commercial dental lamp.
It ha~ been found that the use of p-dialkylamino-benzene~ulphonamides as accelerators, together with camphorquinone in combination with surface-coated glass Le A 26 5~7 - 2 -fillers of a certain degree of silanization, and micro-filler~ and-commercial monomer and auxiliaries leads to filling ma~erials which have a long pot life but, on the other hand, cure rapidly and completely after expo~ure to the light of a dental lamp. Compared with known products, the~e materials do not ~how any deterioration in mechanical properties after ~torage for 2 years.
The light-curing dental compo~ites according to the inventionl in particular tooth filling composites, which contain one or more polymerizable (meth~acrylic compounds, photoinitiators, accelerators, inorganic filler~ and, if desired, conventional auxiliaries are characterized in that they contain:
a) 10-50~ by weight of one or more monomers which contain at least 2 polymerizable ~meth)acrylic acid groups, b) 5-80% by weight of a glass or a glass ceramic which has an average particle diameter of between 0.1 and lO ~m and ha~ been surface-treated with ~-meth-acryloxypropyltrimethoxysilane up to a carbon content of between 0.2 and :2.5% by weight, c) 2-10% by weight of a ~urface--treated microfiller and d) 0.1-5% by weight of a photoactivator consi~ting of a mixture of camphorquinone and p-dialkylamino-benzene~ulphonamide.
Ex~mpla3 of &uitable monomers are as ~ollows:
Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, l,12-dodecanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dime~h-acrylate, 2,2-bi~(p-(2'-hydroxy-3'-methacryloyloxy-Le A 26 557 - 3 -propoxy)phenyl)propane, 2,2-bis(p-(2'-methac~yloyloxy-ethoxy)phenyl)propane, trLmethylolpropane tri(meth)-acrylate, bis-(meth)acryloyloxyme~hyl)-tricyclo-[5.2.1.0Z6]decane according to Genman Offenlegungsschrift 2,931,925 and German Offenlegungsschrift 2,931,926, 1,3-di((meth)acryloyloxypropyl)-1,1,3,3-tretramethyl-disiloxane ana 1,3-bis(3-(me~h)acryloyloxyethylcarbamoyloxy-propyl)-1,1,3,3-te~r~nethyldisiloxane. MonomexR which at 13 mbar have a boilin~ point of mere than 100C are particularly preferred.
In the context of the pre~ent inYention, it i9 preferred to use mixtures of different (meth)acrylates according to the in~ention.
It is also possible to use mixtures of monomers which contain several comonomers.
Preferred light-curing dental composites accord-ing to the invention, in particular tooth filling com-posites t which contain one or more polymerizable (meth)-acrylic compound~, photoinitiators, accelerators, inorganic fillers and, if desired, conventional au~iliar-ies are characterized in that they contain a) 10-30~ by weight of one or more monomers which contain at least 2 polymerizable (meth)acrylic acid groups, b) 40-75~ by weight of a glas or a glass ceramic which ha~ a partlcle size of between 0.1 and 10 ~m and has been post-treated with ~-methacryloxypropyl~ri-methoxysilane up to a carbon cont~nt of between 0.5 and 2.5~ by weight, Le A 26 557 ~ 4 ~
c) 2-10% by weigh~ of a surface trea~ed microfiller and d) 0.1-5% by weight of a photoactivator consi~ting o a mix~ure of camphorquinone and p-dialkylamino-~enzenesulphonamide.
The examples which follow demonstrate the ad-vantages of the compo3ites according to the invention.
As already mentioned, the essential fQature ~f a plastic filling material is a sufficiently long pot life in combination with rapid and complete curing on exposure to the light of a dental lamp. This means that the polymerization depths should be as large as po sible. An inhibition layer on the ~urface of the cured pla~tic, which becomes visible as a ~trong surface discoloration in a test according to "Revi~ion of ISO 4049/1978"/ is a disadvantage; it must be avoided. Thu~, the optLmum composite sh~uld have long pot lives in ambient light, rapid and complete curing on exposure to the light of a dental lamp and no surface discoloration. This require-ment is met by the plastic ~illing materials according to the invention.
Example 1 (comparative e~ample3 1000 ~ of pa~te contain:
Bisphenol A diglycidyl dimethacrylate (BIS GMA): 128.725 g Triethylene glycol dimetha~rylate (TEGDMA) 105.330 g Surface-treated Ba glass filler, a~erage particle diameter 1.3 ~m 762.225 g Camphorquino~e/diethylaminoethyl acrylate a~ ~tar~er sy~tem: 1.010 g Auxil~rie~ and additives: 2.710 g Le A 26 55? 5 (2.38 g of ~TINUVIN P, 0.33 g of ~IONOL) Pot life of the paste in ambient light measured in accordance with DIN propoæal 0013922: 150 s Polymerization depth after an exposure of 60 s to the light of a dental lamp:6.5 mm Inhibition layer on the surf ace of the cured plastic filling material determined by a te~t as provided in "Revi~ion of ISO 40 49/1978 " I yes xample 2 (comparative ex~mple) 1000 g of paste containo BIS GMA; 62.00 g TEGDMA; 62.00 g Surface-treated Zn glass filler, average particle diameter 2.3 ~m 875.00 g ~uxiliari 5 and additives: 1.44 g (1.26 g of ~TINWIN P, 0.18 g of ~IONOL) Camphorquinone N,N-dLmethylamino-p-hydroxy-ethylbenzene as staxter system: 1.30 g Pot life of the paste in ambient light measuxed in accordance with DIN proposal 0013g~2: 50 s Polymerization depth after an exposure of 60 s to the light of a dental l~mp:5.9 mm Inhibition layer on the surface of the cured pla~tic filling mat~rial determined by ~ test a~ provided in "Revi~ion of ISO 4049/lg78"; yes Ex~mple 3 (compara~ive example) 1000 g ef paste contain~
BIS phenol~A PO/hex~methylene diisocyanate- 74.25 g ~EGDMA: 60.75 ~
.
Le_A 26 557 - 6 -2C3~ 7 Surface-treated Ba glass filler, average particle diameter 3 ~m 862.03 g ~uxiliarie~ and additi~es: 1.56 g (1.37 g of ~TINUVIN P, 0.19 g of ~IONOL) Camphorquinone/diethylaminoethyl methacrylate a~ starter sy~tem: 1.41 g Pot life of the ~aste in ambient light measured in accordance with DIN proposal 0013922: 30 5 Polymerization depth after an expo~ure of 60 ~ to the light of a dental l~mp: 6.5 mm Inhibition layer on the surface of ~he cured plastic filling material determined by a test a~ provided in "Revision of ISO 4049/1978": no Example 4 (comparative example) 1000 ~ of pa~te contain.
BIS GMA; 71.00 g TEGDM~; 71.00 g Surface-treated Zr ceramic filler, average par~icle diameter 2 ~m 854.83 g Auxiliaries and additi~e~: 1.65 g (1.45 g of ~TINUVIN P, 0.~0 g of ~IONOL) Camphorquinone N,N-dimethylamino-p-hydroxy-ethylbenzene (pre~ent in the monomer) 1.52 g Pot life of the paste in ambient light mea~ured in accordance with DIN propo~al 001392~: 15 s Pol~erization depth after an exposure of 60 5 to ~he light of a dental lamp: 4.7 mm Le A 26 S57 - 7 -z~
Inhibition layer on the surface of the cured plastic filling material determined by a test as provided in "Revision of ISO 404~/1978": no Example 5 (according to the invention) 1000 g of paste contain:
BIS GMA; 172.015 g TEGDMA; 74.008 g Surface-treated Ba glas~ filler, average particle diameter 1.2 ~m 749.486 g Camphorquinone/diallylsulphonamide as ~tarter sy~tem: 1.641 g ~uxiliaries and additives: 2.850 g (2.50 g of ~TINWIN P, 0.35 g of ~IONOL) Pot life of th~ pa~te in ambient light mea~ured in accord~nce with DIN proposal 0013922: 100 Polymerization depth after an exposure of 60 ~ to the light of a dental lamp: 7.7 mm Inhibition layer on the ~urfac~ of the cured plastic fillin~ material determined by a test a~ provided in "Revision of ISO 4049/1978": no The example~ listed clearly show that the com-posite according to the invention tExample 5) which contain3 ~he new starter system camphorquinone/diallyl 2~ suphonamide in combination with the surfacs-coated glass filler~ of a cer~ain degree of s.ilanization mee~s the required conditions. In addition to a long pot life in ambien~ light, rapid and complete curing ic achieved on exposure to the light of a dental lamp, while the cured plasti~ filling material does not ~how a ~urface di~-Le A 26 557 - 8 -2~ r~
coloration.
The material accordin~ to com-parative Example 1 ha a very long pot life in ambienk light, but the curing depths on exposure to the light of a dental lamp are small and at the same tlme a thick inhibition layer is iormed on the surface of the cured material.
The material~ according to ~xample~ 2, 3 and 4 have very short pot lives under ambient light.
The weight ratio of camphorquinone to diallyl-sulphonamide advantageously is from 4:1 to 1:4 and prefer-ably from 2:1 to 1:2.
It will be appreciated that the instant specification and claims are set forth by way of illustration and not limitation and that various modifications and changes may be made without departing from the spirit and scope of the present invention.
g _
Claims (2)
1. In a dental composite containing a polymer-izable (meth)acrylic compound, photoinitiator, acceler-ator, inorganic filler and conventional auxiliaries, the improvement wherein the composite by weight comprises about a) 10-50% of at least one monomer which contains at least 2 polymerizable (meth)acrylic acid groups, b) 5-80% of 2 glass or a glass ceramic which has an average particle size of between about 0.1 and 10 µm and has been post-treated with .gamma.-methacryloxy-propyltrimethoxysilane up to a carbon content of between about 0.5 and 2.5% by weight, c) 2-10% of a surface-treated microfiller and d) 0.1-5% of a photoactivator consisting of a mixture of camphorquinone and p-dialkylamino-benzenesulphonamide.
2. A dental composite accordinq to claim 1, by weight comprising about a) 10-30% of at least one monomer which contains at least 2 polymerizable (meth)acrylic acid groups, b) 40-75% of a glass or a glass ceramic which has an average particle size of between about 0.1 and 10 µm and has been post-treated with .gamma.-methacryloxy-propyltrimethoxysilane up to a carbon content of between about 0.5 and 2.5% by weight, c) 2-10% of a surface-treated microfiller and d) 0.1-5% of a photoactivator cosisting of Le A 26 557 - 10 -a mixture of camphorquinone and p-dialkylamino-benzenesulphonamide.
Le A 26 557 - 11 -
Le A 26 557 - 11 -
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3903734.7 | 1989-02-09 | ||
| DE3903734 | 1989-02-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2009471A1 true CA2009471A1 (en) | 1990-08-09 |
Family
ID=6373653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002009471A Abandoned CA2009471A1 (en) | 1989-02-09 | 1990-02-07 | Hybrid plastic filling material |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5028638A (en) |
| EP (1) | EP0382033A3 (en) |
| JP (1) | JPH03197407A (en) |
| CN (1) | CN1044823A (en) |
| AU (1) | AU628477B2 (en) |
| CA (1) | CA2009471A1 (en) |
| NO (1) | NO900348L (en) |
| PT (1) | PT93074A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5338773A (en) * | 1993-04-19 | 1994-08-16 | Dentsply Research & Development Corp. | Dental composition and method |
| US5502087A (en) | 1993-06-23 | 1996-03-26 | Dentsply Research & Development Corp. | Dental composition, prosthesis, and method for making dental prosthesis |
| US5876210A (en) | 1994-04-22 | 1999-03-02 | Dentsply G.M.B.H. | Dental polymer product |
| US5955514A (en) | 1993-04-19 | 1999-09-21 | Dentsply Research & Development Corp. | Dental composition and method |
| US5981620A (en) | 1993-04-19 | 1999-11-09 | Dentsply Research & Development Corp. | Dental compounds, compositions, products and methods |
| US5998499A (en) | 1994-03-25 | 1999-12-07 | Dentsply G.M.B.H. | Liquid crystalline (meth)acrylate compounds, composition and method |
| US6353061B1 (en) | 1993-05-26 | 2002-03-05 | Dentsply Gmbh | α, ω-methacrylate terminated macromonomer compounds |
| US6369164B1 (en) | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
| US6391940B1 (en) | 1993-04-19 | 2002-05-21 | Dentsply Research & Development Corp. | Method and composition for adhering to metal dental structure |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3903407A1 (en) * | 1989-02-06 | 1990-08-09 | Blendax Werke Schneider Co | DENTAL FUELING MATERIAL |
| US5268396A (en) * | 1990-11-02 | 1993-12-07 | Lai Juey H | Organosilicon soft denture liners |
| EP0486775B1 (en) * | 1990-11-17 | 1994-11-23 | Heraeus Kulzer Gmbh | Polymerisable dental material |
| DE4110612C2 (en) * | 1990-11-17 | 1995-10-19 | Heraeus Kulzer Gmbh | Polymerizable dental material |
| US5362769A (en) * | 1992-05-07 | 1994-11-08 | Ormco Corporation | Orthodontic adhesives |
| DE4334211C2 (en) * | 1993-10-07 | 2000-08-03 | Heraeus Kulzer Gmbh & Co Kg | Process for the production of a finely divided inorganic filler in the form of a composite filler made of macro-filler particles and micro-filler particles and its use |
| US5348476A (en) * | 1993-11-24 | 1994-09-20 | Essential Dental Systems, Inc. | System for fabrication of dental cast post and core using a burn-out post |
| US5750590A (en) * | 1995-02-22 | 1998-05-12 | Heraeus Kulzer Gmbh | Polymerizable material |
| DE19615763C2 (en) * | 1996-04-20 | 1999-10-28 | Heraeus Kulzer Gmbh & Co Kg | Silica-based filler, process for its preparation and its use |
| US6180688B1 (en) | 1997-12-15 | 2001-01-30 | Ivoclar Ag | Ion-releasing composite material |
| DE19757647C2 (en) * | 1997-12-15 | 2003-10-23 | Ivoclar Vivadent Ag | Ion-releasing composite material |
| DE10253481B4 (en) | 2002-11-13 | 2007-11-15 | Voco Gmbh | Composite material and use of a composite material |
| EP2361601A1 (en) * | 2010-02-25 | 2011-08-31 | 3M Innovative Properties Company | Glass and/or glass ceramic particles containing composition for application on a dental article, process and use thereof |
| KR102228118B1 (en) * | 2019-02-12 | 2021-03-16 | 주식회사 하스 | Dentistry composite comprising a Glass-ceramics |
| CN110755270A (en) * | 2019-10-22 | 2020-02-07 | 华南理工大学 | Dental composite resin containing branched polysiloxane (methyl) acrylate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089763A (en) * | 1973-04-24 | 1978-05-16 | Imperial Chemical Industries Limited | Method of repairing teeth using a composition which is curable by irradiation with visible light |
| EP0060911B1 (en) * | 1981-03-24 | 1985-06-19 | Blendax-Werke R. Schneider GmbH & Co. | Dental filling material |
| DE3135113A1 (en) * | 1981-09-04 | 1983-03-24 | Bayer Ag, 5090 Leverkusen | PHOTOPOLYMERISABLE MASSES, THEIR USE FOR DENTAL PURPOSES, AND METHOD FOR THE PRODUCTION OF DENTAL SPARE PARTS, FILLING AND COATING |
| US4544359A (en) * | 1984-01-13 | 1985-10-01 | Pentron Corporation | Dental restorative material |
| EP0166009A1 (en) * | 1984-06-22 | 1986-01-02 | Dentsply Gmbh | Photopolymerizable dental composition for preparing crowns and bridges |
-
1990
- 1990-01-22 US US07/468,049 patent/US5028638A/en not_active Expired - Fee Related
- 1990-01-25 NO NO90900348A patent/NO900348L/en unknown
- 1990-01-28 EP EP19900101680 patent/EP0382033A3/en not_active Ceased
- 1990-02-05 JP JP2024564A patent/JPH03197407A/en active Pending
- 1990-02-05 AU AU49288/90A patent/AU628477B2/en not_active Ceased
- 1990-02-07 PT PT93074A patent/PT93074A/en not_active Application Discontinuation
- 1990-02-07 CA CA002009471A patent/CA2009471A1/en not_active Abandoned
- 1990-02-09 CN CN90100606A patent/CN1044823A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5338773A (en) * | 1993-04-19 | 1994-08-16 | Dentsply Research & Development Corp. | Dental composition and method |
| US5955514A (en) | 1993-04-19 | 1999-09-21 | Dentsply Research & Development Corp. | Dental composition and method |
| US5981620A (en) | 1993-04-19 | 1999-11-09 | Dentsply Research & Development Corp. | Dental compounds, compositions, products and methods |
| US6391940B1 (en) | 1993-04-19 | 2002-05-21 | Dentsply Research & Development Corp. | Method and composition for adhering to metal dental structure |
| US6500879B1 (en) | 1993-04-19 | 2002-12-31 | Dentsply Research & Development Corp. | Dental composition and method |
| US6339114B1 (en) | 1993-05-26 | 2002-01-15 | Dentsply Detrey Gmbh | Liquid crystalline (meth)acrylate compounds, composition and method |
| US6353061B1 (en) | 1993-05-26 | 2002-03-05 | Dentsply Gmbh | α, ω-methacrylate terminated macromonomer compounds |
| US6369164B1 (en) | 1993-05-26 | 2002-04-09 | Dentsply G.M.B.H. | Polymerizable compounds and compositions |
| US5502087A (en) | 1993-06-23 | 1996-03-26 | Dentsply Research & Development Corp. | Dental composition, prosthesis, and method for making dental prosthesis |
| US5554665A (en) * | 1993-06-23 | 1996-09-10 | Dentsply Research & Development Corp. | Method and dispenser for making dental products |
| US5998499A (en) | 1994-03-25 | 1999-12-07 | Dentsply G.M.B.H. | Liquid crystalline (meth)acrylate compounds, composition and method |
| US5876210A (en) | 1994-04-22 | 1999-03-02 | Dentsply G.M.B.H. | Dental polymer product |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0382033A2 (en) | 1990-08-16 |
| NO900348L (en) | 1990-08-10 |
| JPH03197407A (en) | 1991-08-28 |
| NO900348D0 (en) | 1990-01-25 |
| PT93074A (en) | 1990-08-31 |
| CN1044823A (en) | 1990-08-22 |
| AU628477B2 (en) | 1992-09-17 |
| AU4928890A (en) | 1990-08-16 |
| EP0382033A3 (en) | 1991-04-10 |
| US5028638A (en) | 1991-07-02 |
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